(1) Field of the Invention
This invention relates to a process for producing a phenyl ester in a high yield and stably by allowing benzene, a carboxylic acid and a molecular oxygen to react with each other in the presence of a specific palladium catalyst. It also relates to the specific palladium catalyst used in the process for the production of a phenyl ester.
(2) Description of the Related Art
A process for producing a phenyl ester by allowing benzene, a carboxylic acid and molecular oxygen to react with each other in the presence of a catalyst is well known. Proposals have been made wherein the reaction is conducted in the vapor phase or liquid phase using a noble metal catalyst. Palladium is most popularly used as the main ingredient of the noble catalyst, and some proposals also have been made wherein a co-catalyst comprising a metal, which exhibits by itself no catalytic activity for the specified reaction, is used in combination with the noble catalyst.
As examples of the process using a metal catalyst, there can be mentioned a process using at least one metal selected from palladium and platinum, described in Japanese Examined Patent Publication (hereinafter abbreviated to xe2x80x9cJP-Bxe2x80x9d) S46-33024, a process using a combination of at least one metal selected from palladium and platinum with elemental bismuth or tellurium, described in JP-B S48-18219. Further, a process using a catalyst comprising a combination of palladium or a palladium compound with at least one compound comprising a metal selected from cadmium, zinc, uranium, tin, lead, antimony, bismuth, tellurium and thallium, and in the presence of nitric acid is described in JP-B S55-15455.
A catalyst system comprising palladium and antimony, and an alkali metal salt as an activation promotor is described in JP-B 56-21463, Japanese Unexamined Patent Publication (hereinafter abbreviated to xe2x80x9cJP-Axe2x80x9d) S52-27089, JP-A S52-77892 and JP-A S52-130494.
Further, as examples of the process using a metal compound as catalyst, there can be mentioned a process using a catalyst comprising a combination of at least one metal compound selected form an oxide, a hydroxide, an acetate or a nitrate of a metal selected from platinum, palladium, rhodium, ruthenium, iridium, or osmium, with at least one alkali metal nitrate (JP-B S50-34544), a process using a combination of (a) at least one member selected from metallic palladium and palladium compounds, with (b) at least one compound selected from nitric acid, nitrous acid and metal salts of these acids, or a combination of (a), (b) with (c) at least one metal salt of a carboxylic acid (JP-A S48-4439, and a process using a combination of palladium acetate with antimony acetate, and at least one metal acetate, the metal of which is selected from chromium, nickel, manganese and iron (JP-B H2-13653)
The processes for allowing benzene, a carboxylic acid and molecular oxygen to react with each other in the liquid phase using palladium catalyst or a palladium compound catalyst to produce a phenyl ester have a problem such that palladium metal is dissolved in the raw material liquid, and the catalytic activity is reduced with time. Palladium is expensive and thus the above processes are costly. If a step of recovering palladium is conducted, the production processes become complicated. Further, the operation of compensating the decrease of catalytic activity with time is troublesome and not advantageous from an industrial point of view.
In a process using a metal salt catalyst soluble in a reaction liquid, a step of recovering the metal salt must be conducted. Further, a problem arises such that, for example, a palladium salt is used, palladium metal is liable to be deposited on the inner wall of a reactor during the reaction, and this also leads to reduction of catalytic activity with time and loss of palladium.
A process comprising a liquid phase reaction using as a catalyst a combination of palladium with bismuth and/or lead wherein a soluble bismuth compound and/or a soluble lead compound is additionally incorporated in the reaction system is described in JP-A S63-174950. In this process, the soluble bismuth compound and/or the soluble lead compound prevents dissolution of metallic bismuth or lead supported on the palladium catalyst, and thus, dissolution of the main catalyst ingredient, i.e., palladium can be suppressed and the reduction with time of catalytic activity can be minimized. This process has a problem such that the amount of the soluble bismuth compound and/or the soluble lead compound incorporated is large, and the soluble compounds must be recovered as a crystal at the step of separating and purifying a phenyl ester, which leads to complication of the production process.
In view of the foregoing prior art, an object of the invention is to provide a process for producing a phenyl ester by allowing benzene, a carboxylic acid and molecular oxygen to react with each other in the presence of a palladium catalyst to produce a phenyl ester, whereby a high catalytic activity is maintained and a phenyl ester can be produced under stable conditions.
In accordance with the present invention, there is provided a process for producing a phenyl ester which comprises the step of:
allowing benzene, a carboxylic acid and molecular oxygen to react with each other in the presence of a catalyst comprising:
(A) palladium,
(B) at least one element selected from the group consisting of elements of groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table, and
(C) at least one element selected from the group consisting of elements of groups 3, 4 and lanthanoid elements of the periodic table.
Palladium (A) and element (B), which is at least one member selected from elements of groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table, are used preferably in a metallic state. Palladium (A) and element (B) selected from groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table may form together an intermetallic compound.
Element (B) is not particularly limited provided that it is selected from groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table. Usually element (B) is selected from those belonging to the fourth to sixth periods. Of these, lead, bismuth, antimony and tellurium are preferable. Among the elements of groups 13, 14, 15 and 16 and the fourth to sixth periods, those of group 16 are preferable. The ratio of element (B) to palladium is usually in the range of 0.01/1 to 20/1 by mol, preferably 0.02/1 to 2/1 by mol. When the ratio of element (B)/Pd is too small or too large, the effect of the invention becomes difficult to obtain.
Element (C), which is at least one element selected from the group consisting of elements of groups 3, 4 and lanthanoid elements of the periodic table, is preferably used in a metal oxide form. A part of element (C) may be in a metal form. Element (C) may form an intermetallic compound together with at least one of palladium (A) and element (B).
When the catalyst of the invention is supported on a carrier which is inactive to the reaction, element (C) selected from groups 3, 4 and lanthanoid elements of the periodic table may form a double oxide together with the carrier. When the catalyst of the invention is used without being supported on a carrier which is inactive to the reaction, at least one of palladium (A) and element (B) may be used in a form of being supported on a metal oxide comprising element (C), i.e., at least one element selected from groups 3, 4 and lanthanoid elements of the periodic table.
Element (C) is not particularly limited provided that it is selected from groups 3, 4 and lanthanoid elements of the periodic table. Usually element (C) is selected from those belonging to the fourth to sixth periods. Of these, yttrium, lanthanoid elements, titanium, zirconium and hafnium are preferable. Cerium, praseodymium, neodymium, titanium, zirconium and hafnium are especially preferable. The amount of element (C) is usually in the range of 0.1% to 99.99% by weight, preferably 1% to 99% by weight, based on the total weight of the catalyst. If the relative amount of element (C) is too small, the effect of the invention is difficult to obtain. In contrast, if the relative amount of element (C) is too large, the relative amount of the main catalyst ingredient, i.e., palladium, is reduced and the effect of the invention also is difficult to obtain.
The raw material for palladium (A) used is not particularly limited, and includes palladium metal and palladium compounds such as, for example, ammonium hexachioropalladate, potassium hexachloropalladate, sodium hexachioropalladate, ammonium tetrachloropalladate, potassium tetrachloropalladate, sodium tetrachloropalladate, potassium tetrabromopalladate, palladium oxide, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium acetate, potassium dinitrosulfite-palladate, chlorocarbonyl palladium, dinitrodiamminepalladium, tetraaminepalladium chloride, tetraamminepalladium nitrate, cis-diamminedichloropalladium, trans-dianminedichloro-palladium, dichloro (ethylenediamine) palladium, potassium tetracyanopalladate and acetylacetonatopalladium.
The raw material for element (B) is not particularly limited provided that it contains an element selected from groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table. As specific examples of the raw material for element (B), there can be mentioned metallic lead and lead compounds such as lead acetate, lead chloride, lead fluoride, lead iodide, lead nitrate, lead oxide, lead sulfate, lead oxalate, lead naphthenate and lead stearate; metallic bismuth and bismuth compounds such as bismuth chloride, bismuth nitrate, bismuth oxychloride, bismuth acetate and bismuth oxide; metallic antimony and antimony compounds such as antimony fluoride, antimony chloride, antimony bromide, antimony iodide, antimony acetate, antimony methoxide, antimony ethoxide, antimony isopropoxide, antimony butoxide, antimony ethylene glycoxide, antimony potassium tartrate, antimony oxide, antimony sulfide, and complex compounds with an organic acid such as tartaric acid or oxalic acid; and metallic tellurium and tellurium compounds such as tellurium chloride, tellurium oxide, tellurium iodide and telluric acid.
The raw material for element (C) is not particularly limited provided that it contains an element selected from groups 3, 4 and lanthanoid elements of the periodic table. As specific examples of the raw material for element (C), there can be mentioned metallic cerium and cerium compounds such as cerium fluoride, cerium chloride, cerium bromide, cerium iodide, cerium acetate, cerium nitrate, ammonium cerium nitrate, diammonium cerium nitrate, cerium oxide, cerium sulfate, ammonium cerium sulfate, tetraammonium cerium sulfate, cerium carbonate, cerium oxalate and cerium acetylacetonate; metallic praseodymium and praseodymium compounds such as praseodymium acetate, praseodymium fluoride, praseodymium chloride, praseodymium nitrate, praseodymium oxide and praseodymium oxalate; metallic neodymium and neodymium compounds such as neodymium acetate, neodymium fluoride, neodymium chloride, neodymium nitrate, neodymium oxide, neodymium carbonate, neodymium oxalate and neodymium acetylacetonate; metallic titanium and titanium compounds such as titanium carbide, titanium chloride, titanium oxide, titanium sulfate, potassium titanium oxalate, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide and titanium 2-ethyl-hexanolate; metallic zirconium and zirconium compounds such as zirconium chloride, zirconium oxychloride, zirconium oxide, zirconium oxynitrate, zirconium tetraisopropoxide, zirconium tetrabutoxide, zirconium acetylacetoflate and zirconium naphthenate; and metallic hafnium and hafnium compounds such as hafnium chloride and hafnium oxide.
The amount of palladium (A) used is usually in the range of 0.01% to 10% by weight, preferably 0.1% to 5% by weight, based on the total weight of the catalyst. If the amount of palladium is smaller than 0.01% by weight, the rate of reaction is apt to be reduced. In contrast, if the amount of palladium is larger than 10%, the effect of the invention is not further enhanced and it is not advantageous from cost consideration.
The procedure by which the catalyst is prepared is not particularly limited. When the catalyst is supported on a carrier, a conventional procedure may be employed, which includes, for example, impregnation, ion exchange, precipitation and kneading procedures.
The carrier used for supporting the catalyst of the invention may be prepared by a conventional procedure. When the supported catalyst is prepared, a raw material for element (C) selected from groups 3, 4 and lanthanoid elements of the periodic table may be first combined with the carrier. For example, a co-precipitation procedure may be employed, in which a solution of a raw material for element (C) is treated with a precursor compound for the carrier whereby hydrolysis is caused to form a co-precipitate in the form of a double oxide. Then palladium (A) and element (B) selected from groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table are supported on the double salt.
When a carrier which is inert itself to the intended reaction is not used, a raw material for element (C) selected from groups 3, 4 and lanthanoid elements of the periodic table may be first converted to a metal oxide by a conventional procedure, and then, palladium (A) and element (B) selected from groups 13, 14, 15 and 16 and the fourth to sixth periods of the periodic table may be supported on the metal oxide.
When the catalyst ingredients (A), (B) and (C) are supported on a carrier by an impregnation procedure, the carrier may be allowed to support either simultaneously these ingredients (A), (B) and (C), or, support first one of the ingredients (A), (B) and (C) and then the other ingredients.
According to the conventional impregnation or ion exchange procedure, the carrier having the as-supported catalyst is subjected to decantation, filtration, heating or vacuum-heating to remove the solvent used. Thereafter the catalyst-supported carrier is dried, for example, by heating or under a reduced pressure.
The dried catalyst supported on a carrier is subjected to a reduction treatment to activate the catalyst ingredient. Prior to the reduction treatment, the dried catalyst may be calcined. The calcination is carried out usually at a temperature of 200 to 700xc2x0 C. in an oxygen-containing atmosphere such as oxygen, air or a mixture of oxygen with nitrogen, helium or argon.
The reduction treatment can be carried out by a conventional procedure. For example, a vapor phase reduction procedure using a reducing agent such as hydrogen, carbon monoxide, ethylene or methanol, or a liquid phase reduction procedure using a reducing agent such as hydrazine hydrate, formalin or formic acid. The vapor phase reduction treatment is carried out usually at a temperature of 100 to 700xc2x0 C., preferably 100 to 600xc2x0 C.
The carboxylic acid to be reacted with benzene and molecular oxygen includes those which have not larger than 10 carbon atoms. As specific examples of the carboxylic acid, there can be mentioned monocarboxylic acids such as acetic acid, propionic acid and butyric acid, and dicarboxylic acids such as adipic acid. Lower monocarboxylic acids having up to 6 carbon atoms such as acetic acid and propionic acid are preferable.
The amount of the carboxylic acid is not particularly limited, but is preferably in the range of 0.1 to 100 moles per mole of benzene.
The molecular oxygen used as an oxidizing agent in the process of the invention may be either pure oxygen or diluted with an inert gas such as nitrogen, helium or argon, and air may be used. The optimum amount of oxygen varies depending upon the reaction temperature, the amount of catalyst and other factors, and is not particularly limited provided that the gas composition flowing through a catalyst-packed bed is out of the explosive range.
Benzene, carboxylic acid and molecular oxygen are allowed to react with each other in the presence of the catalyst in the liquid phase, vapor phase or vapor-liquid mixed phase. The reaction apparatus is not particularly limited. For example, a fixed bed flow-through type reactor, a batch reactor and suspension bed reactor can be used.
The amount of the catalyst used varies depending upon the particular reaction procedure and is not particularly limited. For cost consideration, in the case where a fixed bed type reactor is used, the amount of the catalyst is usually in the range of 0.1 to 50 hxe2x88x921, preferably 0.1 to 30 hxe2x88x921, as liquid hourly space velocity (LHSV), i.e. as the total feed volume rate of benzene plus carboxylic acid per unit volume of the catalyst and per unit time (hr). In the case where a suspension bed type reactor is used, the concentration of the catalyst is preferably in the range of 0.05 to 30% by weight based on the total weight of benzene and carboxylic acid.
The reaction temperature is usually in the range of 100 to 300xc2x0 C., preferably 100 to 250xc2x0 C. The reaction pressure is normal pressure or higher, usually in the range of normal pressure to 200 atmospheric pressures, and preferably normal pressure to 100 atmospheric pressures.
The reaction time varies depending upon the reaction temperature and pressure, the amount of catalyst and the manner in which reaction is performed, and is not particularly limited. For example, when the reaction is performed in a batchwise or semi-batchwise manner, the reaction time is usually at least 0.5 hour. When the reaction is performed in continuous manner using a suspension bed or a fixed bed, the residence time is usually in the range of 0.03 to 10 hours.
Phenol can be easily produced from the phenyl ester obtained by the process of the invention. The procedure for producing phenol may be conventional and the reaction occurring for the production of phenol includes, for example, hydrolysis reaction and ester exchange reaction.
According to the process of the invention, the catalyst activity can be maintained at a high level, and a phenyl ester which is useful as a raw material for phenol can be stably produced.